Density functional study of the adsorption of propene on mixed gold-silver clusters, AunAgm:: Propensity rules for binding

We use density functional theory to investigate the binding of propene to small mixed Au-Ag clusters, in the gas phase. We have found that the rules proposed by us for propene binding to Au and Ag clusters, also work for binding to mixed Au-Ag clusters. The rules state that propene binds to those sites on the edge of the cluster where the equal density plots of the LUMO of the naked cluster protrude into the vacuum. Furthermore, the desorption energy of propene correlate with the LUMO energy: the lower the LUMO energy, the stronger the propene bond. We have also found an additional rule that is specific to mixed clusters. We call active the atoms on which the LUMO of the naked cluster protrude in the vacuum, and inactive those for which such protrusions do not exist. To define the rules we use the following notation: A is an active site to which propene is bound B is another active site, and C is an inactive site. If the atom in C (Ag or Au) is replaced with another atom (Au or Ag) propene desorption energy changes very little. If we replace the atom B with a more electronegative atom (i.e., we replace Ag by Au) the propene bond to A becomes stronger. If we replace the atom B with a less electronegative atom (i.e., we replace Au by Ag) the propene bond to A becomes weaker. (C) 2004 American Institute of Physics.